Preparation of betaine hydrochloride, etc.



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This invention relates to the manufacture of betaine hydrochloride,glutamic acid and otash salts, from the residual liquors ot the eetsugar industry remaining after the separation and recovery of availablesugar from the molasses.

llt has heretofore been proposed to treat the concentrated residualliquors with an excess r hydrochloric acid. suficient in amount toellect the precipitation oil betaine hydrochloride, glutamic acid andpotassium chloride. Such processes require acid-resistant all all

apparatus together with a considerable excess of hydrochloric acid,suficient to saturate the solution.

According to the present invention, the use of such an excess ofhydrochloric acid is avoided.- l have found that the use of such anexcess of acid is not necessary and that betaine hydrochloride andpotassium chloride, either without or with glutamic acid hydrochloride,can be readily separated from the concentrated residual liquor by theaddition to the acidified liquor of a chloride which is more soluble inwater than potassium chloride, such as calcium chloride, magnesiumchloride or ammonium chloride. l have tound that the addition oil suchchlorides to the acidified liquor brings about a salting out of theconstituents mentioned.

lit the acidified solution is allowed to become hot, or is'heated to asuficiently high temperature, glutamic acid hydrochloride will be formedand recipitated along with betainehydrochlori e and potassium chloride.ll, however, the solution is lrept cool during the process, the glutamicacid rydrochloride is not precipitated but betaine chloride andpotassium chloride are precipitated. This precipitation is moreovereffected from a solution which does not contain any large excess olhydrochloric or other acid. The equipment used, therefore, does not needto be resistant against such an excess of acid. Large amounts of acidscan also be avoided with resulting economy.

Where the process is carried out in the cold, and where betaine h'drochloride and inorganic chlorides are rst precipitated, these may beseparated by filtration and the mother liquor then heated to around 80(1. or higher to hydrolyze the glutamic acid compounds in the liquor, e.g., glutamine. By neutralizing-the solution with soda or withapplication tiled .J'uly it, iaaa lain No. iaaaa other basic material tohydrogenion concentraiton just neutral to methyl orange, the glutamlcacid is precipitated since it is nearly insoluble in such a solution.The glutamic acid prepared in this way may be purified by dissolving itin a small amount of dilute hydrochloric acid and reprecipitating it bymaking the solution neutral to methyl orange.

The invention will be further illustrated by the following specificexample of the procedure followed in efiecting the separation of thepotassium salts, betaine hydrochloride and glutamic acid from the'desaccharified molasses. The parts are by weight.

Concentrated. Stefiens" waste-water, or other desaccharified beetmolasses, having a specific gravity between T29 and 1.42, is made acidto thymol blue by the addition of a strong acid, such as sulfuric,phosphoric, or hydrochloric acid. The solution'is contilt stantlystirred during addition of the acid in order to prevent the heat formedduring neutralization from heating any portion oil the solution above C.Sevent parts of powdered anhydrous calcium ch oride are then added foreach 100 parts of water present in the solution. This addition is mosteasily effected by heating the solution. to 50 The mother liquor fromthe mixed crystals v of betaine hydrochloride and inorganic chloridesmay advantageously be used for the preparation oil glutamicacid. Thismay be lit effected by hydrolyzing the glutamic acid compound (probablyglutamine) contained in the solution by heating the liquor to 80- C. foreighteen hours or longer. lBeing soluble in acidified solutions, theglutarnic acid remains in solution. It is precipitated' by addingcaustic soda or other base until the solutlon is neutral to methylorange. The glutamic acid may be recovered by filtration.

When prepared in this manner, the glutamic acid is light brown. It maybe purified by dissolving it in a little dilute hydrochloric acid,filtering the resultant solution, and reprecipitating the glutamic'acidby making the solution neutral to'methyl orange.

Other chlorides, e. g., magnesium, aluminum or ammonium chloride may beused for the salting out of the betaine hydrochloride and in organicchlorides. In any case, suflicient of the chloride is added to saturatethe Water, contained in the desaccharified molasses, at the temperatureat which the solution is filtered.

In case calcium chloride is available in solu tion instead of in theanhydrous solid form, the procedure may advantageously be modified andcarried out as follows:

Sufficient strong acid (hydrochloric, sulfuric, phosphoric or otheracid) is added to concentrated Steffens waste, or other desaccharifiedbeet molasses, to make the solution slightly acid to litmus. Twentyparts of calcium chloride in solution is added for each 100 parts of drySteffens waste contained in the solution, and the solution is evaporateduntil it just remains liquid when cooled to room temperature. Sufficientstrong hydrochloric acid is then added to'make the solution acid tomethyl orange. After the crystallization of the potassium and sodiumchlorides and the betaine hydrochloride, the crystals are filtered offand the betaine hydrochloride extracted therefrom with methanol, asdescribed above. Glutamic acid may be recovered from the mother liquor,after the crystallization of the sodium and potassium chlorides, and ofthe betaine hydrochloride, according to the procedure above described.

Among the advantages which the process of the present invention presentsmay be mentioned the followiirg:A nearly quantitative separation ofbetaine hydrochloride, potassium salts and glutamic acid is effectedfrom the sugars, organic acids, etc. which constitute the residue of thedesaccharified molasses. The betaine hydrochloride and glutamic acid canbe separated in a pure form from the desaccharified molasses without theuse of expensive organic solvents. No large amount of acid is requiredto effect the precipitation of the salts nor are the solutions stronglyacid at any time during the process so that acid-resistant apparatusneed not be used I claim:

1. The method of treating concentrated residual liquors of beet molasseswhich comprises adding a mineral acid and a soluble chloride to theconcentrated liquors.

2. The method of treating concentrated residual liquors of beet molasseswhich comprises adding to the liquor an acid in sufficient amount toacidify the liquor and also adding thereto a soluble chloride insufficient amount to precipitate betaine hydrochloride therefrom.

3. The method of treating concentrated residual liquors of beet molasseswhich comprises adding t o the liquor an acid in sulficient amount toacidify the liquor and also adding thereto a soluble chloride insufficient amount to precipitate betaine hydrocloride therefrom, andsubsequently heating the mother liquor and neutralizing the liquor toprecipitate glutamic acid therefrom.

4. The method of treating residual liquor from beet molasses whichcomprises acidifying the concentrated liquor and adding calcium chloridethereto in sufiicient amount to precipitate betaine hydrocloride andpotassium chloride.

5. The method of treating concentrated rcsidual liquors of beet molasseswhich comprises adding thereto hydrochloric acid and a soluble chloride.4

6. The method of treating concentrated residual liquors of beet molasseswhich comprises adding to'the liquor hydrochloric acid in sufiicientamount to acidify the liquor and also adding thereto asoluble chloridein sufficient amount to precipitate betaine hydrochloride therefrom.

7. The method of treating concentrated residual liquors of beet molasseswhich com prises adding to the liquor hydrochloric acid in sufficientamount to acidify the liquor and also adding thereto a soluble chloridein sufficient amount to precipitate betaine hydrochloride therefrom, andsubsequently heating the mot-her liquor and neutralizing the liquor toprecipitate glutamic acid therefrom.

8. The method of treating residual liquor from beet molasses whichcomprises acidlfying the concentratedliquor with hydrochloric acid andadding calcium chloride thereto in sufficient amount to precipitatebetaine hydrochloric and potassium chloride.

In testimony whereof I afiix my signature.

DONALD K. TRESSLER.

